Aluminum titanium chloride composition



United States Patent ()fiice 3,061,410 Patented Oct. 30, 1962 This invention relates to a new composition of matter useful as such either as a dehydrating agent in certain specialized uses or as a smoke screen producer, and as a component of catalytic compositions capable of catalyzing the polymerization of low molecular weight olefins to produce high molecular weight polymers.

This application is a continuation-in-part of my copending application Serial No. 631,021, filed December 28, 1956, and now abandoned, for Aluminum Titanium Tetrachloride Composition.

The composition of the present invention is a solid consisting of aluminum, titanium, and chlorine, and containing these elements in proportions corresponding to the empirical formula (AlTi Cl where n is at least unity. The composition may be prepared by reacting elemental aluminum and titanium tetrachloride at moderately elevated temperature, preferably in a hydrocarbon medium.

The following example will illustrate the preparation of the composition of the invention:

Example I A 250 ml. stirred reactor was flushed with nitrogen to remove elemental oxygen. 100 ml. of mixed hexanes and stoichiometric amounts of titanium tetrachloride and 7 aluminum required for AlTizClg were then introduced into the reactor. The stoichiometric amounts were 18.98 grams (0.1 mol) of titanium tetrachloride and 1.35 grams (0.05 gram atom) of aluminum powder. The reactor was then closed and twice flushed with nitrogen at 200 p.s.i.g. The nitrogen was then vented from the reactor to reduce the internal pressure to approximately atmospheric. The reactor was then sealed and heated to 120 C. The contents were held at this temperature and stirred for 16 hours. 'The reactor was then cooled and flushed .with nitrogen. No elemental chlorine had been evolved during the reaction. The reactor was then transferred to a dry boxewhich was flushed with nitrogen to remove air and water vapor. The reactor was then opened and its contents were filtered to separate a hydrocarbon -fil.- trate and a solid filter cake. The filter cake was washed with mixed hex-anes, dried in a nitrogen atmosphere, and bottled while still in the nitrogen atmosphere. 19.19 grams of a solid product were obtained.

' The above solid product was determined to be where n is at least unity, by subjecting the solid to a number of analyses, tests and observations, and by evaluating the findings, as follows:

(7) Content of titanium trichloride as suchnone, both from X-ray diffraction studies and from the fact that the solid in water forms a pale grey-colored solution and results in no evolution of gas, whereas titanium trichloride in water forms a deep bluecolored solution and hydrolyzes, with the evolution of gas.

Content of titanium dicholoride as suchnone, both from X-ray difiraction studies and from the fact that placing the solid in water results in no evolution of gas, whereas titanium dichloride in water reacts with the water to form TiOCl and hydrogen gas.

(9) X-ray difiracnon studies:

(a) X-ray diffraction pattern- Line 20 dA I Percent I/I max.

(b) Findings, from X-ray difiraction pattern: high surface area, no lines for aluminum chloride, titanium dichloride or titanium trichloride.v

(10) Amount of potassium permanganate that reacts with p the so1id--2.22 milliequivalents. This was .deter- "mined by reacting 0.2984 gram of the solid with excess 0.0995 N potassium permanganate with 0.1022 N sodium thiosulfate. Theoretical amount of potassium permanganate necessary to oxidize the titanium in AlTi Cl to tetravalent titanium- 2.21 milliequivalents. ll) Solubility in mixed hexanes, cyclohexane, Decalin, white oil, carbon tetrachloride, p-dichlorobenzene,

o-dichlorobenzene, chlorobenzene, titanium tetra chloride, antimony trichloridenone.

Solubility in etherslight.

Solubility in water-rapid and complete decomposition of solid.

(14) Reaction with air and with water vapor--rapid,

- with evolution of volatile products.

Melting point from heating-mot determinable; decomposes both upon heating in the presence of air and upon heating in a vacuum.

.(17) .Ratio of aluminum content to titanium tetrachloride content-stoichiometric amounts necessary for AlTi Cl (18) Conclusion: The solid is (AlTi Cl where n is at least unity.

The Example I preparation of'the composition of the invention illustrates the preferred method. tAny liquid hydrocarbon may be substituted for the hexanes; aliphatic, cyclo'aliphatic, and aromatic hydrocarbons being preferred. The preparation is preferably made at temperatures in the range 80 to 200 C., employing sufiicient pressure to maintain the hydrocarbon 'in liquid phase. With a stoichiometric excess of TiCl, over aluminum, the TiCl and aluminum combine in the stoichiometric amounts for AlTizclg; evaporation of the unreacted TiCl 'at the conclusion of the reaction leaves the same solid product obtained when the reaction is conducted using stoichiometric amounts in the first instance. It appears possible to make the preparation without the hydrocarbon diluent, but if this procedure is attempted, the temperature should be kept below about 150 C. There is, however, considerable advantage in using the hydrocarbon as described; its presence facilitates control of the reaction and recovery of the desired product.

When the solid prepared as in Example I and a strongly anionic agent, such as lithium aluminum hydride, trialkyl aluminums, lithium hydride, sodium hydride, trialkyl borons, boron hydrides, dialkyl magnesiums, sodium alkyls or sodium aluminum hydride, are dispersed in an inert, nonpolar liquid, the resulting mixture catalyzes the polymerization of many u-olefins, including propylene, to produce solid polymers. Also, a dispersion of the solid and a strongly cationic'reagent such as titanium tetrachloride, titanium trichloride, aluminum chloride, boron trifluoride, dialkyl aluminum chloride, 'alkyl aluminum dichloride, vanadium trichloride, zirconium chloride, or silicon tetrachloride, in an inert nonpolar liquid will catalyze polymerization of ethylene to produce a solid polymer.

The employment of the composition of the invention as a component of a polymerization catalyst is illustrated in the following example, wherein propylene is polymerized.

Example II A 360 milliliter rocking bomb was flushed with nitrogen to remove air and water vapor and charged with 100 m1. of mixed hexanes, 1.0 gram of an AlTi Cl solid prepared as in Example I and 0.5 gram of LiAlH powder. The bomb was closed and flushed three times with nitrogen at 200 p.s.i.g. Nitrogen was bled from the bomb to atmospheric pressure and 37 grams of Phillips 99% propylene was introduced. The bomb was sealed and heated with shaking for 1 hour. During the last half of this period, the temperature was .in the range 71 to 87 C. and the pressure was in the range 180t'o 130 p.s.i.g. The shaking was interrupted and an additional 15 grams of propylene was introduced into the bomb, which was then heated and shaken for 2% hours. The temperature and pressure during thisperiod were 92-97 C. and-l30 2l5 p.s.iLg. The shaking wa's interrupted and an additional .15 grams of propylene were inagain with water.

troduced into the bomb, which was again heated with shaking for a further period of 1 hour, the temperature and pressure being maintained in the same range as during the preceding 2 /2 hour period. The bomb was then cooled to atmospheric temperature, vented to permit escape of unreacted propylene, and flushed with nitrogen. The contents of the bomb were immersed in 400 cc. of isopropyl alcohol and the resulting mixture was heated on a steam plate for 1 hour, during which the volume was reduced to ml. 300 ml. of water and 100 m1. of 12 N hydrochloric acid were then added to the beaker, which was heated on a steam plate for 1 hour. At the end of this period the contents of the beaker were filtered and the filter cake was washed with water. The filter cake was then ground to a'powder in a Waring Blendor and resuspended in 300 ml. of water, 100 ml. of 12 N hydrochloric acid and 100 ml. of 2-propanol. The suspension was heated for 1 hour and filtered. The filter cake was washed with water, with dilute ammonia, and The filter cake was then extracted with diethyl ether to remove amorphous polymer. After the extraction 28 grams of dry, solid crystalline polymer remained. The ether washings were diluted with methanol and water. The amorphous polymer contained in the ether separated out as a gummy mass which was separated, dried, and weighed. The weight of the amorphous polymer was 11.62 grams.

The solid crystalline polymer had a melting range of to 163 C. It was pressed between thin glass discs at C. to produce a film. The film was transparenttranslucent and very tough. The intrinsic viscosity of the solid polymer was determined in tetralin at 155 C. and was found to be 2.76 dl./=gram.

Solid polyethylene is produced when AlTi Cl and certain Friedel-Crafts type catalysts are dispersed in mixed hexanes and the resulting mixture is contacted with ethylene under conditions similar to those employed in the above polymerization of propylene.

The solid prepared as in Example I is (AlTi Cl where n is at least unity; there is of course no distinction chemically between AlTi Cl and (A1Ti Cl if the material does not exist in solution, as here. In such case the value of n, and therefore the molecular weight, is a function of the size of the solid crystal; the crystal in effect is all one molecule.

.1 claim:

As a new composition of matter, a reddish-purple amorphous-appearing solid compound in substantially pure form having the formula (AlTi Cl wherein n is an integer, characterized by a rapid decomposition in water with no evolution of a gas, and an X-ray diffraction pattern possessing the following dominant d-spacings in angstroms: 5.9, 5.2, 2.9, 2.5, 1.77, and 1.13.

References Cited in the file of this patent UNITED STATES PATENTS 2,745,735 Byrns May .15, 1956 2,745,802 Schmidt May 15, 1956 2,765,270 Brenner Oct. 2, 1956 2,835,568 Kingsbury May 20, 1958 2,880,199 Jezl Mar. 31, 1959 2,928,818 Carter et al Mar. 15, 1960 

